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Search for "intermolecular" in Full Text gives 794 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Unique halogen–π association detected in single crystals of C–N atropisomeric N-(2-halophenyl)quinolin-2-one derivatives and the thione analogue
Beilstein J. Org. Chem. 2025, 21, 1748–1756, doi:10.3762/bjoc.21.138
- N-(2-bromo- or 2-chlorophenyl)quinolin-2-ones, homochiral layered polymers, which consist of (P)- or (M)-atropisomers, were formed through intermolecular halogen–π association. The halogen–π association in the racemates is due to a halogen bond (C–X···π) between a σ-hole on the halogen atom and a π
- C–N atropisomers and their structural properties for over 25 years [16][17]. As a part of the C–N atropisomeric chemistry, we succeeded in the asymmetric synthesis of mebroqualone (I) and the thione analogue II [18][19]. In the course of this study, it was found that intermolecular association in
- through a σ-type intermolecular halogen bonding (C–Br···O) between the ortho-bromine atom and the carbonyl oxygen. The formation of similar heterochiral polymers through a σ-type intermolecular halogen bond (C–Br···S) was also found in crystals of the thio-analogue rac-II. On the other hand, in the
Thermodynamics and polarity-driven properties of fluorinated cyclopropanes
Beilstein J. Org. Chem. 2025, 21, 1742–1747, doi:10.3762/bjoc.21.137
- providing the greatest stability due to strong anomeric-like interactions that enhance electron delocalization. Notably, the all-cis-1,2,3-trifluorocyclopropane (1.2.3-c.c.) was identified as the most polar compound, with its Janus-like electrostatic potential enabling unique intermolecular interactions
Approaches to stereoselective 1,1'-glycosylation
Beilstein J. Org. Chem. 2025, 21, 1700–1718, doi:10.3762/bjoc.21.133
- selectivity in glycosylations with various types of nucleophiles [67][68]. This remarkable stereoselectivity has been attributed to intermolecular hydrogen bonding, which forms a transient tether between the glycosyl donor and acceptor, thereby guiding the reaction towards a preferred stereochemical outcome
Synthesis of optically active folded cyclic dimers and trimers
Beilstein J. Org. Chem. 2025, 21, 1603–1612, doi:10.3762/bjoc.21.124
- same absolute configuration. The |glum| value of 7 was 0.4 × 10−3 (Figure S18A, Supporting Information File 1), which was lower than that of 6. In the case of the film states of 6 and 7, low PL brightness and intermolecular random orientation of fluorophores resulted in noisy CPL signals. The CD
3-Aryl-2H-azirines as annulation reagents in the Ni(II)-catalyzed synthesis of 1H-benzo[4,5]thieno[3,2-b]pyrroles
Beilstein J. Org. Chem. 2025, 21, 1595–1602, doi:10.3762/bjoc.21.123
- reactions of intermolecular annulation of a variety of non-aromatic five- [4][5][6] and six-membered carbo- and heterocycles [7][8][9] with azirines, which occur under transition metal catalysis or photocatalysis. Annulation of the pyrrole ring to an aromatic system is limited to reactions of functionalized
- formation of the C–C bond between the rings of the reacting molecules occurs in the coordination metal sphere as an intra-, rather than intermolecular, process. The formation of compound 17, the product of oxidative dimerization of indole-based enol 15, in the second reaction also points to different
Highly distinguishable isomeric states of a tripodal arylazopyrazole derivative on graphite through electron/hole-induced switching at ambient conditions
Beilstein J. Org. Chem. 2025, 21, 1496–1507, doi:10.3762/bjoc.21.112
- (≈120°), the angle between the vectors. The intermolecular distance obtained from STM corresponds to the lateral length of the EEE isomer (F to F distance is 22.06 Å). Thus, we conclude that the adlayer is formed by the energetically most favorable EEE isomer. This is also consistent with the NMR data
- is not a surprise [10][36]. Therefore, it is summarized that the typical intermolecular interactions are of van der Waals type and interactions dominantly driven by steric packing. We note that the STM experiments reveal only a hexagonal type of arrangement of molecules, as shown in Figure 3
Advances in nitrogen-containing helicenes: synthesis, chiroptical properties, and optoelectronic applications
Beilstein J. Org. Chem. 2025, 21, 1422–1453, doi:10.3762/bjoc.21.106
- versatile scaffolds for chiral optoelectronic applications. The incorporation of nitrogen enables precise modulation of electronic structures, redox characteristics, and intermolecular interactions, thereby enhancing performance in circularly polarized luminescence (CPL), thermally activated delayed
- structures, enhance solubility, and expand functional diversity [6]. Substituting carbon atoms with electron-deficient nitrogen atoms introduces new opportunities to fine-tune redox potentials, charge-transport behavior, and intermolecular interactions [7]. These modifications have proven especially valuable
- , attributed to intermolecular hydrogen bonding with solvent molecules. With increasing helical length, both the λabs and λem exhibit progressive bathochromic shifts, while the ФF values systematically decline, without clear saturation within the investigated range. Chiroptical measurements of the N-butylated
Tautomerism and switching in 7-hydroxy-8-(azophenyl)quinoline and similar compounds
Beilstein J. Org. Chem. 2025, 21, 1404–1421, doi:10.3762/bjoc.21.105
- reasons are different. While in acetonitrile this is the effect of the increased polarity of the solvent, leading to stabilization of the more polar keto tautomers, in the non-polar chloroform it is caused by its proton-donative nature (formation of a stabilizing intermolecular hydrogen bonding with the C
Reactions of acryl thioamides with iminoiodinanes as a one-step synthesis of N-sulfonyl-2,3-dihydro-1,2-thiazoles
Beilstein J. Org. Chem. 2025, 21, 1397–1403, doi:10.3762/bjoc.21.104
- involved in the formation of a weak intermolecular hydrogen bond of the C‒H···N≡C type with distances H(3)···N(3) 2.53(3) Å, C(3)···N(3) 3.436(4) Å and angle C(3)H(3)N(3) 157(2)° (symmetry transformation [1−x, 1−y, 1−z]). Conclusion Thus, we found that thioamides of acrylic acid easily interact with
Oxetanes: formation, reactivity and total syntheses of natural products
Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101
- greatly exploited in the past [34] and new protocols are still being developed and reported. These reactions can be divided into intramolecular and intermolecular processes and they usually rely on oxygen- or nitrogen-based nucleophiles, but ring openings involving hydrides and soft carbon nucleophiles
- –2021, Kuduk and co-workers published three different tandem, one-pot methodologies towards complex polycyclic heterocycles [100][101][102]. All of them are two-step reactions consisting of an intermolecular coupling followed by an intramolecular, base-induced oxetane opening (Scheme 48). The first one
Recent advances in amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer
Beilstein J. Org. Chem. 2025, 21, 1306–1323, doi:10.3762/bjoc.21.100
- of amidyl radicals as HAT reagents, with a particular emphasis on their role in the intermolecular HAT process. We highlight key developments, mechanistic insights, and emerging strategies that harness the unique reactivity of amidyl radicals in the selective functionalization of a variety of
- activation energy modulation during transition state formation. Specifically, donor/acceptor electronic configurations in the substrate could either stabilize or destabilize the transient hybrid state, thereby thermodynamically governing the energy barrier for intermolecular HAT progression. When the partial
- insight in the development of novel methods for amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer. Although, amidyl radicals employed in many reactions as HAT reagents via heating conditions have been summarized in several studies [52][53][54][55][56][57][58]. To advance
Recent advances and future challenges in the bottom-up synthesis of azulene-embedded nanographenes
Beilstein J. Org. Chem. 2025, 21, 1272–1305, doi:10.3762/bjoc.21.99
- and co-workers [55]. A palladium-catalysed variation of [3 + 2] annulation, accompanied by ring expansion [56], was used for the intermolecular reaction between acenes bearing alkyne substituents 55a–d and di-n-butylacetylene (56). The reaction gave a series of azulene-embedded isomers of linear
Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents
Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98
- oxidant and initiator, enabling an efficient intermolecular cascade cyclization process (Scheme 5) [5]. In this strategy, a novel, selective, metal-free synthetic method was introduced for the synthesis of isoxazoline-featured oxindoles through iminoxyl radical-promoted cascade oxyalkylation
- elimination or single-electron oxidation and deprotonation, yielding the final oxindole products 81 and regenerating the Pd(0) catalyst I. In the same year, Zhang’s group developed a novel visible-light-induced palladium-catalyzed intermolecular radical cascade cyclization of N-arylacrylamides with
- for constructing quaternary carbon centers in oxindoles via an N-heterocyclic carbene (NHC)-catalyzed intermolecular Heck-type alkyl radical addition and annulation reaction (Scheme 47) [28]. The reaction proceeds through a redox-neutral mechanism, where the NHC catalyst serves a dual role as both a
Supramolecular assembly of hypervalent iodine macrocycles and alkali metals
Beilstein J. Org. Chem. 2025, 21, 1095–1103, doi:10.3762/bjoc.21.87
- bonding is characterized as those interactions that involve intermolecular hypervalent connections with lengths shorter than the sum of the van der Waals radii between a heavy p-block element and an electron-pair donor (typically O, N, S, or halogen) [15]. Secondary I···O interactions have been found to
Recent advances in synthetic approaches for bioactive cinnamic acid derivatives
Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85
- styrenes with alkyl formates and the oxidant 4-cyano-1-(1-methylethoxy)pyridinium trifluoromethanesulfonate to give the corresponding cinnamate esters 185–192 via intermolecular addition of styrene to an alkoxyradical forming radical adduct 193 (Scheme 59) [102]. Iwasawa and co-workers (2020) employed CO2
- )-cinnamic acid esters 445–448 in excellent yields via E-to-Z photoisomerization mediated by the photocatalyst (Scheme 90) [152]. Nguyen and co-workers (2019) employed iodine to catalyze the intermolecular olefin-carbonyl metathesis reaction of benzaldehyde (449) and acrylate 450 to give the corresponding
Recent advances in controllable/divergent synthesis
Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73
- achieved selective synthesis of either enantiomer of a target product by controlling the reaction duration (Scheme 13) [42]. When performing the asymmetric intermolecular allylic amination of 6-hydroxyisoquinoline (49) with tert-butyl(1-phenylallyl)carbonate ((rac)-50) using an Ir catalyst derived from [Ir
Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion–π interactions
Beilstein J. Org. Chem. 2025, 21, 884–889, doi:10.3762/bjoc.21.72
- , while the glycol chains are oriented along the long axis in the opposite orientations. In packing mode, the submacrocycle units form close contacts through intermolecular hydrogen bonding, C–H···π, and lone pair–π interactions, resulting in a 1D linear assembly. Anion recognition With the functional
Light-enabled intramolecular [2 + 2] cycloaddition via photoactivation of simple alkenylboronic esters
Beilstein J. Org. Chem. 2025, 21, 854–863, doi:10.3762/bjoc.21.69
- process (Figure 2B) [19]. In a bid to translate sensitization reaction probes to meaningful synthetic transformations, conventional intermolecular [2 + 2] cycloaddition reactions were initially trialled (Figure 3A). Preliminary reactions using styrene or methyl acrylate were unsuccessful, with no [2 + 2
- ] cycloaddition observed, despite the use of higher catalyst loadings. The efficient isomerization of 1a during these reactions indicated that substrate lifetime for efficient intermolecular reactivity may be problematic. While substrate-tethered reactivity, developed by Brown and co-workers was unsuccessful [49
- as an operational mechanism. While intermolecular alkene quenching to enable [2 + 2] cycloaddition was inefficient, presumably due to poor substrate lifetime, intramolecular [2 + 2] reactivity with both acrylates and alkenylboronic esters was effective. The small 3D, boron-containing fragments could
Unraveling cooperative interactions between complexed ions in dual-host strategy for cesium salt separation
Beilstein J. Org. Chem. 2025, 21, 845–853, doi:10.3762/bjoc.21.68
- six Cs–O ion-dipole interactions (2.9 Å and 3.2 Å). These intermolecular interactions of Cs+ cations with18-crown-6 and hexaurea receptors help to form 3D framework in the solid state (Supporting Information File 1, Figure S2), which may reinforce cooperative interactions between complexed Cs+ and
- with 18-crown-6 and tripodal receptor (CCDC: 2411575) and (b) chemical structures for three types of intermolecular interactions with complexed Cs+. (c) IGM plot illustrating the attraction between complexed Cs+ and complexed phosphate. Color coding in the range of −0.5 < ρ sign(λ2) < 0.5 a.u. Atom
Development and mechanistic studies of calcium–BINOL phosphate-catalyzed hydrocyanation of hydrazones
Beilstein J. Org. Chem. 2025, 21, 755–765, doi:10.3762/bjoc.21.59
- –(Ca) five-ring. This initial product is consumed in a tautomerization step to give slightly more stable 11, in which the cyanide group is no longer bound to the calcium atom. Tautomerization 10 → 11 (with Nβ hydrogen shifting to Nα, the former imine nitrogen) is most likely intermolecular, as direct
Copper-catalyzed domino cyclization of anilines and cyclobutanone oxime: a scalable and versatile route to spirotetrahydroquinoline derivatives
Beilstein J. Org. Chem. 2025, 21, 749–754, doi:10.3762/bjoc.21.58
- to generate an enamine intermediate. Subsequently, an intermolecular cyclization occurs between the enamine and imine intermediates, ultimately yielding the final target product through an aromatization process (Scheme 4). Conclusion In summary, we have developed an efficient and practical copper
- intermediates, followed by intermolecular cyclization and aromatization. The scalability of this method was demonstrated through a gram-scale reaction, highlighting its potential for practical applications in medicinal chemistry and drug discovery. Synthetic strategies for the construction of
Origami with small molecules: exploiting the C–F bond as a conformational tool
Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54
- molecules’ intermolecular interactions too. The intramolecular H-bond makes the hydroxy group a weaker intermolecular H-bond donor [104] (e.g., 55 vs 54, Figure 8). This runs counter to a longstanding assumption [105] that the inductive effect of fluorine should always make the hydroxy group a stronger H
- -bond donor. For non-rigid molecules, the greater the population of intramolecularly H-bonded conformers, the worse the hydroxy group will be as an intermolecular H-bond donor [106]. To be clear, fluorine can make the hydroxy group a stronger intermolecular H-bond donor in certain circumstances, for
- instance in highly-fluorinated alcohols (e.g., hexafluoroisopropanol) [107], or in rigid molecules where intramolecular H-bonding is not possible [104] (e.g., 56, Figure 8); but it is not a universal phenomenon. The issue of intra- vs intermolecular H-bonding of vicinal fluorohydrins can complicate matters
Photochemically assisted synthesis of phenacenes fluorinated at the terminal benzene rings and their electronic spectra
Beilstein J. Org. Chem. 2025, 21, 670–679, doi:10.3762/bjoc.21.53
- wavelength region for the corresponding parent phenacenes whereas their fluorescence bands markedly red-shifted and broadened. These observations suggest that the intermolecular interactions of excited-state F8-phenacene molecules are significantly different from those of the corresponding parent molecules
- - and 13-fluoropicene, formed dimeric structures through intermolecular F∙∙∙H contacts and behaved as p-channel semiconductors. By contrast, little information is available about the effects of polyfluorination on the physical properties and structures of phenacenes. It is expected that polyfluorination
- processes contributing to the low fluorescence quantum yield of the F8-phenacenes (cf. Table 1). Because fluorescence behavior in the solid state reflects molecular alignment and intermolecular interactions in the crystals, solid-state fluorescence of the F8-phenacenes was investigated. We observed
Deep-blue emitting 9,10-bis(perfluorobenzyl)anthracene
Beilstein J. Org. Chem. 2025, 21, 515–525, doi:10.3762/bjoc.21.39
- for material scientists [12][13][14]. One of the structural features favorable for an efficient anthracene-based blue emitter is the introduction of bulky substituents in the 9 and 10 positions, which results in a solid-state packing with limited π–π intermolecular interactions, which, in turn, tends
- to suppress undesirable fluorescence self-quenching [15]. Not only do bulky substituents disrupt intermolecular interactions of this type, they can also provide higher chemical stability and reduce or prevent the photodimerization and photo-oxidation to which all acenes are prone [13]. Furthermore
Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye
Beilstein J. Org. Chem. 2025, 21, 500–509, doi:10.3762/bjoc.21.37
- crystalline compounds significantly enhances the stereoselectivity and yield of topochemical reactions compared to those conducted in solution [10]. A key requirement for these reactions is the intermolecular distance between the two reactive double bonds. Schmidt’s rule, which governs topochemical [2 + 2
- optimized, which can only be predicted computationally – a process that becomes increasingly complex with more intricate structures [12]. Since these reactions depend on both crystal packing and specific intermolecular distances, another key challenge lies in designing novel structures capable of undergoing
- conventions. Although these dyes have been known since 1978, their photochemistry has only been briefly explored. In this work, during the synthesis of a series of these dyes (Figure 2a), we observed an unprecedented intermolecular [2 + 2] cycloaddition of syn-(ethoxycarbonyl,chloro)bimane (Cl2B), seen in
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